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在氮掺杂多孔碳纤维中,ZrO 量子点作为化学配体稳定高密度 Cu 活性位,用于高效 ORR。

Stabilizing High Density Cu Active Sites with ZrO Quantum Dots as Chemical Ligand in N-doped Porous Carbon Nanofibers for Efficient ORR.

机构信息

Key Laboratory of Textile Science & Technology, Ministry of Education, College of Textiles, Donghua University, Shanghai, 201620, China.

Department of Materials Science and Engineering, National University of Singapore, Singapore, 117574, Singapore.

出版信息

Small. 2023 Apr;19(15):e2206823. doi: 10.1002/smll.202206823. Epub 2023 Jan 11.

Abstract

The emerging transition metal-nitrogen-carbon (MNC) materials are considered as a promising oxygen reduction reaction (ORR) catalyst system to substitute expensive Pt/C catalysts due to their high surface area and potential high catalytic activity. However, MNC catalysts are easy to be attacked by the ORR byproducts that easily lead to the deactivation of metal active sites. Moreover, a high metal loading affects the mass transfer and stability, but a low loading delivers inferior catalytic activity. Here, a new strategy of designing ZrO quantum dots and N-complex as dual chemical ligands in N-doped bubble-like porous carbon nanofibers (N-BPCNFs) to stabilize copper (Cu) by forming CuZrO /ZrO heterostructures and CuN ligands with a high loading of 40.5 wt.% is reported. While the highly porous architecture design of N-BPCNFs builds a large solidelectrolytegas phase interface and promotes mass transfer. The preliminary results show that the half-wave potential of the catalyst reaches 0.856 V, and only decreases 0.026 V after 10 000 cycles, exhibiting excellent stability. The proposed strategy of stabilizing metal active sites with both heterostructures and CuN ligands is feasible and scalable for developing high metal loading ORR catalyst.

摘要

新兴的过渡金属-氮-碳(MNC)材料由于其高比表面积和潜在的高催化活性,被认为是一种很有前途的氧还原反应(ORR)催化剂体系,可以替代昂贵的 Pt/C 催化剂。然而,MNC 催化剂很容易受到 ORR 副产物的攻击,这很容易导致金属活性位点失活。此外,高金属负载会影响传质和稳定性,但低负载会导致催化活性降低。在这里,我们报道了一种新的策略,即设计 ZrO 量子点和 N-复合物作为双化学配体,用于稳定氮掺杂泡状多孔碳纳米纤维(N-BPCNFs)中的铜(Cu),形成 CuZrO /ZrO 异质结构和 CuN 配体,Cu 的负载量高达 40.5wt.%。同时,N-BPCNFs 的高度多孔结构设计构建了大的固-液-气相间界面,促进了传质。初步结果表明,催化剂的半波电位达到 0.856V,经过 10000 次循环后仅下降 0.026V,表现出优异的稳定性。用异质结构和 CuN 配体稳定金属活性位点的这种策略对于开发高金属负载 ORR 催化剂是可行和可扩展的。

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